Polyfunctional peroxides, vinyl monomer polymerization initiators comprising the same and process for polymerizing vinyl monomers employing the same

ABSTRACT

The novel polyfunctional peroxides are compounds represented by the following general formula (1): 
     
         R.sup.1 --CX.sub.3                                         (1) 
    
     wherein R 1  represents a linear alkyl group having 1 to 3 carbon atoms; and X represents a group: ##STR1## (wherein R 2  represents a linear or branched alkyl group having 1 to 5 carbon atoms). 
     Such polyfunctional peroxides include 1,1,1-tris(t-butylperoxycarbonyloxymethyl)propane and the like. The polymerization initiators for vinyl monomers comprise such polyfunctional peroxides. In the process for polymerizing vinyl monomers, a vinyl monomer is polymerized employing such polyfunctional peroxide at 60 to 160° C.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel polyfunctional peroxide to beutilized as a polymerization initiator for a vinyl monomer, a curingagent and a crosslinking agent for a polymer, a polymerization initiatorcomprising the same and a process for polymerizing a vinyl monomeremploying the same.

2. Description of the Related Art

Polyfunctional peroxides having a plurality of peroxy bonds haveconventionally been employed as polymerization initiators, when highmolecular weight vinyl polymers are to be obtained by subjecting vinylmonomers to bulk polymerization or suspension polymerization.

Various kinds of compounds are so far known as such polyfunctionalperoxides. For example, U.K. Patent No. 1049969 discloses1,1,4,4-tetra(t-butylperoxy)cyclohexane. Japanese Patent Publication No.Sho 40-19013 discloses 2,2-bis (4,4-di(t-butylperoxy)cyclohexyl)propane.Japanese Patent Publication No. Sho 58-56561 disclosestri(t-butylperoxy)triazine. Japanese Patent Publication No. Hei 1-30844discloses tri(t-butylperoxy)trimellitate.

However, these conventional polymerization initiators have lowpolymerization initiation efficiency, so that they have a lowprobability that all of the peroxy bonds which are present in eachmolecule act effectively as the polymerization initiator. Accordingly,the conventional polymerization initiators substantially act as thepolyfunctional initiators at low rates.

More specifically, polymerization mechanism resorting to apolyfunctional peroxide is supposed to operate usually as follows.First, radicals formed by initial cleavage of some of the peroxy bondsin the polyfunctional peroxide are added to the monomer to initiatepolymerization thereof. Thus, a polymer containing peroxy groups isformed. The polymerization initiation efficiency at this initial stageis substantially the same as those of the conventional monofunctionalperoxides.

Next, the peroxide moieties in the polymer are decomposed to formpolymer radicals, which initiate another polymerization to form a highmolecular weight polymer or a branched polymer. However, theconventional polyfunctional peroxides involve a problem that the polymerradicals serving as the polymerization initiator in the second step havelow polymerization initiation efficiency. Accordingly, polyfunctionalpolymerization initiators having higher polymerization initiationefficiency are in demand.

SUMMARY OF THE INVENTION

It is an objective of the present invention to provide a novelpolyfunctional peroxide useful as a polymerization initiator etc.

It is another objective of the invention to provide a polymerizationinitiator for a vinyl monomer, which has peroxy bonds functioningeffectively as the polymerization initiator and also has highpolymerization initiation efficiency.

It is another objective of the invention to provide a process forpolymerizing a vinyl monomer, which can give a high molecular weightvinyl polymer in a high yield, the polymer having a low melt viscosityand excellent molding properties because of its branched structure.

The novel peroxide according to the present invention, in order toattain the objectives described above, is represented by the followinggeneral formula (1):

    R.sup.1 --CX.sub.3                                         (1)

wherein R¹ represents a linear alkyl group having 1 to 3 carbon atoms;and X represents a group: ##STR2## (wherein R² represents a linear orbranched alkyl group having 1 to 5 carbon atoms).

Meanwhile, another novel polyfunctional peroxide is represented by thefollowing general formula (2): ##STR3## wherein R³ represents a linearalkyl group having 1 to 3 carbon atoms; and X represents a group:##STR4## (wherein R⁴ represents a linear or branched alkyl group having1 to 5 carbon atoms).

The features of the present invention that are believed to be novel areset forth with particularity in the appended claims.

The invention, together with the objects and advantages thereof, maybest be understood by reference to the following description of thepresently preferred embodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments of the present invention will be described in detail.

The novel polyfunctional peroxide according to the present invention isa compound represented by the following general formula (1):

    R.sup.1 --CX.sub.3                                         (1)

wherein R¹ represents a linear alkyl group having 1 to 3 carbon atoms;and X represents a group: ##STR5## (wherein R² represents a linear orbranched alkyl group having 1 to 5 carbon atoms).

The polyfunctional peroxide represented by the general formula (1)typically includes, for example,1,1,1-tris(t-butylperoxycarbonyloxymethyl)propane,1,1,1-tris(1,1-dimethylpropylperoxycarbonyloxymethyl)propane,1,1,1-tris(1,1-dimethylbutylperoxycarbonyloxymethyl)propane,1,1,1-tris(1,1,2-trimethylpropylperoxycarbonyloxymethyl)propane,1,1,1-tris (1,1,3, 3-tetramethylbutylperoxycarbonyloxymethyl)propane,1,1,1-tris(cumylperoxycarbonyloxymethyl)propane,1,1,1-tris(t-butylperoxycarbonyloxymethyl)ethane,1,1,1-tris(1,1-dimethylbutylperoxycarbonyloxymethyl)ethane,1,1,1-tris(t-butylperoxycarbonyloxymethyl)butane and1,1,1-tris(1,1-dimethylbutylperoxycarbonyloxymethyl)butane.

More preferred among these polyfunctional peroxides are1,1,1-tris(t-butylperoxycarbonyloxymethyl)propane, 1,1,1-tris(1,1-dimethylbutylperoxycarbonyloxymethyl)propane or1,1,1-tris(1,1,3,3-tetramethylbutylperoxycarbonyloxymethyl)propane. Thatis, in the more preferred polyfunctional peroxides having the generalformula (1), R¹ represents an ethyl group, and R² contained in Xrepresents a methyl group, a n-propyl group or a branched alkyl grouphaving 5 carbon atoms. The reason is that, in such polyfunctionalperoxides, the peroxy bonds in each molecule have high polymerizationinitiation efficiency to exhibit excellent function as thepolymerization initiator.

These polyfunctional peroxides are prepared according to the followingmethod: a corresponding hydroperoxide is reacted with a polyfunctionalchloroformate which is a starting material of the peroxide having thegeneral formula (1) in the presence of an alkali.

The corresponding hydroperoxide includes, for example, t-butylhydroperoxide, 1,1-dimethylpropyl hydroperoxide, 1,1-dimethylbutylhydroperoxide, 1,1,2-trimethylpropyl hydroperoxide,1,1,3,3-tetramethylbutyl hydroperoxide and cumene hydroperoxide.

As the polyfunctional chloroformate, the starting material of theperoxide having the formula (1), there may be employed, for example,trimethylolpropane trischloroformate or trimethylolethanetrischloroformate.

The alkali employable in the reaction includes, for example, sodiumhydroxide, potassium hydroxide, sodium carbonate, sodiumhydrogencarbonate, calcium hydroxide, barium hydroxide, pyridine andtriethylamine. Among others, sodium hydroxide and potassium hydroxideare more preferred, since they can improve the yield of products.

When a polyfunctional peroxide is prepared, a solvent such as ofparaffinic hydrocarbons and aromatic hydrocarbons may also be employed.The reaction is usually carried out at a temperature of 0 to 50° C.,preferably at 5 to 35° C. If the reaction temperature is lower than 0°C., the reaction does not take place sufficiently; whereas at atemperature of higher than 50° C., control of the reaction tends to bedifficult, because the reaction takes place suddenly.

Another novel polyfunctional peroxide according to the present inventionis a compound represented by the following general formula (2): ##STR6##wherein R³ represents a linear alkyl group having 1 to 3 carbon atoms;and X represents a group: ##STR7## (wherein R⁴ represents a linear orbranched alkyl group having 1 to 5 carbon atoms).

The polyfunctional peroxide represented by the general formula (2)typically includes, for example, di(2,2-bis(t-butylperoxycarbonyloxymethyl)butyl) carbonate, di(2,2-bis(1,1-dimethylpropylperoxycarbonyloxymethyl) butyl) carbonate, di(2,2-bis(1,1-dimethylbutylperoxycarbonyloxymethyl)butyl) carbonate,di(2,2-bis(1,1, 2-trimethylpropylperoxycarbonyloxymethyl)butyl)carbonate,di(2,2-bis(1,1,3,3-tetramethylbutylperoxycarbonyloxymethyl)butyl)carbonate, di(2,2-bis(cumylperoxycarbonyloxymethyl)butyl) carbonate,di(2,2-bis (t-butylperoxycarbonyloxymethyl)propyl carbonate anddi(2,2-bis(1,1-dimethylbutylperoxycarbonyloxymethyl)propyl) carbonate.

More preferred among these polyfunctional peroxides aredi(2,2-bis(t-butylperoxycarbonyloxymethyl)butyl) carbonate anddi(2,2-bis (1,1-dimethylbutylperoxycarbonyloxymethyl)butyl) carbonate.That is, in the preferred polyfunctional peroxides having the generalformula (2), R³ represents an ethyl group; and R⁴ contained in Xrepresents a methyl group or a n-propyl group. The reason is that theperoxy bonds in each molecule have high polymerization initiationefficiency to exhibit excellent function as the polymerizationinitiator.

These polyfunctional peroxides are prepared according to the followingmethod: a corresponding hydroperoxide is reacted with a polyfunctionalchloroformate which is a starting material of the peroxide having thegeneral formula (2) in the presence of an alkali.

The corresponding hydroperoxide includes the hydroperoxides as thestarting materials of the peroxides having the general formula (1)exemplified above.

Meanwhile, as the polyfunctional chloroformate, the starting material ofthe polyfunctional peroxide having the general formula (2), there may beemployed, for example, di(2,2-bis(chlorocarbonyloxymethyl)butyl)carbonate and di(2,2-bis(chlorocarbonyloxymethyl)propyl) carbonate.These polyfunctional chloroformates can be obtained as major componentsfrom a polyfunctional chloroformate which is a starting material of thepolyfunctional peroxide having the general formula (1) and acorresponding polyfunctional alcohol under control of reactionconditions.

Accordingly, the starting material of the polyfunctional peroxide havingthe general formula (1) and that of the polyfunctional peroxide havingthe general formula (2) are of the same polyfunctional alcohols. Thepolyfunctional alcohols include, for example, trimethylolpropane andtrimethylolethane.

The alkali employable in the preparation of the polyfunctional peroxidehaving the general formula (2) includes those as listed referring to thepreparation of the polyfunctional peroxide having the general formula(1).

Further, the polyfunctional chloroformate which is a starting materialof the polyfunctional peroxide having the general formula (2) may becontained in the polyfunctional chloroformate which is a startingmaterial of the polyfunctional peroxide having the general formula (1).In this case, the resulting polyfunctional peroxide is a mixture of thepolyfunctional peroxides of the general formula (1) and that of thegeneral formula (2).

Next, the polymerization initiator according to the present invention isa novel peroxide represented by the general formula (1) or (2). As thepolymerization initiator, at least one polyfunctional peroxide selectedfrom these peroxides is usually employed. It is also possible here toemploy a combination of the polyfunctional peroxide of the generalformula (1) and that of the general formula (2). The effects of thesepolyfunctional peroxides (1) and (2) can be exhibited synergisticallydepending on the combination.

As the polymerization initiator, other polymerization initiators may beemployed in addition to the polyfunctional peroxide of the generalformula (1) or (2). When another polymerization initiator is employed,the polymerization rate can be increased. In this case, the molecularweight of the resulting polymer is reduced. Further, a chain transferagent may also be employed additionally. When a chain transfer agent isemployed, the molecular weight of the resulting polymer andpolymerization rate can be adjusted.

A vinyl monomer is polymerized by employing the polymerizationinitiator. described above. The vinyl monomer employable in thepolymerization reaction includes, for example, styrene monomers such asstyrene, α-methylstyrene and vinyltoluene; acrylic monomers such asacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butylacrylate, octyl acrylate, lauryl acrylate, 2-hydroxyethyl acrylate and2-hydroxypropyl acrylate; methacrylic monomers such as methacrylic acid,methyl methacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate, octyl methacrylate, lauryl methacrylate, 2-hydroxyethylmethacrylate and 2-hydroxypropyl methacrylate; and fumaric acid esters,maleic acid esters, acrylonitrile, N-phenylmaleimide, vinyl chloride,vinyl acetate and vinylidene chloride.

The vinyl monomer preferably includes, for example, styrene,α-methylstyrene, acrylonitrile, N-phenylmaleimide, methyl methacrylateand butyl methacrylate. These monomers may be employed singly or as asuitable combination of two or more of them. The monomer combinationsmay be exemplified by styrene and methyl methacrylate; styrene and butylacrylate; styrene and acrylonitrile; styrene and N-phenylmaleimide;styrene and α-methylstyrene; and α-methylstyrene and acrylonitrile.

It is also possible to employ a solution of a rubber such as ofpolybutadiene, styrene-butadiene copolymer, ethylene-propylene copolymeror ethylene-propylene-diene copolymer in such vinyl monomer.

Resins to be obtained from the rubbery components and the monomersinclude, for example, high-impact polystyrene resins (HIPS) consistingof styrene and a butadiene-containing rubber; and high-impactstyrene-acrylonitrile resins (ABS resins) consisting of styrene,acrylonitrile and a butadiene-containing rubber.

Other polymerization initiators employable additionally include, forexample, t-butylperoxyisopropyl monocarbonate,1,1-dimethylbutylperoxyisopropyl monocarbonate,t-butylperoxy-2-ethylhexyl monocarbonate,2,2-bis(4,4-di(t-butylperoxy)cyclohexyl)propane, di-t-butyl peroxide,t-butyl peroxybenzoate and 1,1-dimethylbutyl peroxybenzoate.

The chain transfer agent employable additionally includes, for example,n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan,3-mercaptopropionic acid and an α-methylstyrene dimer.

The polymerization initiator is employed in the polymerization reactionpreferably in an amount of 0.001 to 5 parts by weight, more preferablyin an amount of 0.01 to 1 part by weight in terms of purity per 100parts by weight of the vinyl monomer employed. If the polymerizationinitiator is used in an amount of less than 0.001 part by weight, thepolymerization rate will be reduced; whereas if it is used in an amountof more than 5 parts by weight, the polymerization rate is increased,and control of the polymerization rate tends to be difficult.

Next, referring to the process for polymerizing a vinyl monomeraccording to the present invention, a vinyl monomer is polymerized at atemperature of 60 to 160° C. employing as the polymerization initiatorat least one compound selected from the polyfunctional peroxidesrepresented by the general formula (1) or (2). As a method ofpolymerizing the vinyl monomer, there may be employed bulkpolymerization, solution polymerization or suspension polymerization,and it is also possible to employ a combination of such polymerizationmethods. Further, batchwise polymerization or continuous polymerizationmay also be employed. In the bulk polymerization and suspensionpolymerization of these polymerization methods, vinyl monomers arepolymerized under substantially the same conditions, except for thepresence and absence of water.

The polymerization initiator is employed preferably in an amount of0.001 to 1 part by weight in bulk polymerization, in an amount of 0.01to 2 parts by weight in suspension polymerization, and in an amount of0.01 to 5 parts by weight in solution polymerization, per 100 parts byweight of vinyl monomers employed.

The polymerization temperature is 60 to 160° C. as described above,preferably 80 to 150° C. If the polymerization temperature is lower than60° C., not only the polymerization rate will be reduced, but also allof the peroxy bonds in the polymerization initiator do not decomposebefore completion of polymerization, and thus the initiator does notfunction as a polyfunctional polymerization initiator. Meanwhile, at atemperature higher than 160° C., the polymerization rate is increased tomake adjustment of polymerization rate difficult. Besides, a largeamount of polymerization initiating radicals are formed in a very shorttime. Thus, side reactions between the radicals such as primary radicaltermination occur to lower the polymerization initiation efficiency,consequently.

The solvent employable in solution polymerization includes aromatichydrocarbons such as ethylbenzene, xylene and toluene; ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;alcohols such as isobutanol, n-butanol, ethyl cellosolve and cyclohexylalcohol; esters such as methyl acetate and n-butyl acetate; and ethers.While the amount of such solvent employed is adjusted depending on theconfiguration, performance, etc. of the polymer, it is preferably 1 to80% by weight, more preferably 5 to 50% by weight of the entire polymermixture.

As detailed above, the following effects are exhibited according to theembodiments of the present invention.

(1) The novel polyfunctional peroxide represented by the general formula(1) or (2) is useful as a polymerization initiator and the like.

(2) In the polymerization initiator for vinyl polymers of theembodiment, the peroxy bonds in the polyfunctional peroxide representedby the general formula (1) or (2) function effectively as thepolymerization initiator, so that the polyfunctional peroxide has highpolymerization initiation efficiency.

(3) In the polymerization initiator for vinyl monomers in theembodiment, radicals to be formed in the latter polymerization stepwhere the peroxy bonds in the peroxy bond-containing polymer are cleavedact effectively without loosing their function to maintain highpolymerization initiation efficiency. Accordingly, a branched polymercan be formed effectively.

(4) According to the process for polymerizing a vinyl monomer, a highmolecular weight polymer can be obtained in a high yield, since thepolyfunctional peroxide represented by the general formula (1) or (2)employed as the polymerization initiator has high polymerizationinitiation efficiency and high efficiency as the polyfunctionalinitiator.

(5) According to the process for polymerizing a vinyl monomer, abranched vinyl polymer can be obtained, since a polyfunctional peroxiderepresented by the general formula (1) or (2) is employed as thepolymerization initiator.

(6) According to the process for polymerizing a vinyl monomer, since theresulting branched vinyl polymer has a melt flow index higher than thoseof linear polymers having equivalent molecular weights, the vinylpolymer has a low melt viscosity and excellent molding properties.

EXAMPLES

Next, the present invention will be described more specifically by wayof examples and comparative examples. It should be noted here thatabbreviations used in the following examples stand for the followingcompounds respectively:

TBPP: 1,1,1-tris(t-butylperoxycarbonyloxymethyl)propane

THPP: 1,1,1-tris(1,1-diemthylbutylperoxycarbonyloxymethyl)propane

TOPP: 1,1,1-tris(1,1,3,3-tetramethylbutylperoxycarbonyloxymethyl)propane

TBPD: di(2,2-bis(t-butylperoxycarbonyloxymethyl)butyl) carbonate

THPD: di-(2,2-bis(1,1-dimethylbuthylperoxycarbonyloxymethyl) butyl)carbonate

TBCH: 1,1,4,4-tetra(t-butylperoxy)cyclohexane

BBCP: 2,2-bis(4,4-di(t-butylperoxy)cyclohexylpropane

TBTA: tri(t-butylperoxy)triazine

TBTM: tri(t-butylperoxy)trimellitate.

Example 1

Synthesis of TBPP

To a 1000 ml four-necked flask equipped with a stirrer were introduced96.5 g of a 98% trimethylolpropane trischloroformate and 225 g oftoluene. While the temperature of the resulting mixture was maintainedat 18° C. with stirring, a mixture of 219.0 g of a 30% aqueous potassiumhydroxide solution and 152.6 g of a 70% aqueous t-butyl hydroperoxidesolution was dropped thereto over 30 minutes, and a reaction wascontinued for 90 minutes in the same state. Subsequently, the organiclayer was separated and washed twice with a 5% aqueous sodium hydroxidesolution. The organic layer was further rinsed with water, dehydratedand filtered.

When the organic layer was treated as described above, 312 g of a liquidwas obtained. The concentration of TBPP in the solution was found to be36.7% by measuring the amount of active oxygen, and the yield ofsynthesis based on the starting material chloroformate was 79%. Aportion of the solution was taken as a sample, and the toluene wasremoved therefrom to give a product having a purity of 99%. The productwas then subjected to nuclear magnetic resonance spectrometry (H-NMR) todetect peaks: 0.94 ppm (3H), 1.54 ppm (2H), 4.21 ppm (6H) and 1.33 ppm(27H).

Further, absorption bands corresponding to C═O were observed at 1794cm⁻¹ and 1763 cm⁻¹ by means of infrared (IR) absorption spectrometry.

Elementary analysis of the product gave the following results: carbon(C): 52.44% (theoretical value for TBPP: 52.27%); hydrogen (H): 7.88%(theoretical value for TBPP: 7.94%); oxygen (O): 39.68% (theoreticalvalue for TBPP: 39.79%). The found values of elementary analysis werevery close to the theoretical values respectively. Based on theseresults, the product obtained was identified to be TBPP.

The TBPP thus obtained was further subjected to pyrolysis in benzene ata concentration of 0.01 mol/liter so as to measure the rate ofpyrolysis. The 10-hour half life temperature (the temperature at whichthe amount of active oxygen decreases to 50% in 10 hours, which ishereinafter abbreviated as T10) was 101° C.

Example 2

Synthesis of THPP

A reaction was carried out in the same manner as in Example 1 exceptthat 152.6 g of the 70% aqueous t-butyl hydroperoxide solution wasreplaced with 144.4 g of an aqueous 97% 1,1-dimethylbutyl hydroperoxide.After completion of the reaction, the organic layer was separated andwashed with an aqueous sodium sulfite solution, followed by rinsing withwater, dehydration and filtration, to give 332 g of a liquid. Theconcentration of THPP in the solution was found to be 40.5% by measuringthe amount of active oxygen, and the yield of synthesis based on thestarting material chloroformate was 79%.

A portion of the solution was taken as a sample, and the toluene wasremoved therefrom to give a product having a purity of 97%. The productwas then subjected to nuclear magnetic resonance spectrometry (H-NMR) todetect peaks: 0.94 ppm (3H), 1.53 ppm (2H), 4.21 ppm (6H), 1.28 ppm(18H), 1.59 ppm (6H), 1.55 ppm (6H) and 0.92 ppm (9H). Further,absorption bands corresponding to C═O were observed at 1794 cm⁻¹ and1763 cm⁻¹ by means of infrared (IR) absorption spectrometry.

Elementary analysis of the product gave the following results: carbon(C): 57.49% (theoretical value for THPP: 57.23%); hydrogen (H): 8.68%(theoretical value for THPP: 8.89%); oxygen (O): 33.83% (theoreticalvalue for THPP: 33.88%). The found values of elementary analysis werevery close to the theoretical values respectively. Based on theseresults, the product obtained was identified to be THPP.

T10 of the THPP thus obtained measured in benzene at a concentration of0.01 mol/liter was 97° C.

Example 3

Synthesis of TOPP

A reaction was carried out in the same manner as in Example 2 exceptthat 144.4 g of the 97% aqueous 1,1-dimethylbutyl hydroperoxide wasreplaced with 180.6 g of a 96% aqueous 1,1,3,3-tetramethylbutylhydroperoxide to give 348 g of a liquid. The concentration of TOPP inthe solution was found to be 43.2% by measuring the amount of activeoxygen, and the yield of synthesis based on the starting materialchloroformate was 77%.

A portion of the solution was taken as a sample, and the toluene wasremoved therefrom to give a product having a purity of 96%. The productwas then subjected to nuclear magnetic resonance spectrometry (H-NMR) todetect peaks: 0.94 ppm (3H), 1.54 ppm (2H), 4.21 ppm (6H), 1.37 ppm(18H), 1.64 ppm (6H) and 1.03 ppm (27H). Further, absorption bandscorresponding to C═O were observed at 1794 cm⁻¹ and 1763 cm⁻¹ by meansof infrared (IR) absorption spectrometry.

Elementary analysis of the product gave the following results: carbon(C): 61.36% (theoretical value for TOPP: 60.90%); hydrogen (H): 9.58%(theoretical value for TOPP: 9.60%); oxygen (O): 29.06% (theoreticalvalue for TOPP: 29.50%). The found values of elementary analysis werevery close to the theoretical values respectively. Based on theseresults, the product obtained was identified to be TOPP.

T10 of the TOPP thus obtained measured in benzene at a concentration of0.01 mol/liter was 93° C.

Example 4

Synthesis of TBPD

A reaction was carried out in the same manner as in Example 1 exceptthat 96.5 g of the 98% trimethylolpropane trischloroformate was replacedwith 122.4 g of a 90% di(2,2-bis (chlorocarbonyloxymethyl)butyl)carbonate. The rest (10%) of the chloroformate solution wastrimethylolpropane trischloroformate. Thus, 326 g of a liquid wasobtained. The concentration of TBPD in the solution was found to be39.3% by measuring the amount of active oxygen, and the yield ofsynthesis based on the starting material carbonate was 75%.

The solution was treated to give a product having a purity of 93%, andthen the product was subjected to nuclear magnetic resonancespectrometry (H-NMR) to detect peaks: 0.94 ppm (6H), 1.54 ppm (4H), 4.23ppm (8H), 4.21 ppm (4H) and 1.33 ppm (36H). Further, absorption bandscorresponding to C═O were observed at 1794 cm⁻¹ and 1763 cm⁻¹ by meansof infrared (IR) absorption spectrometry.

Elementary analysis of the product gave the following results: carbon(C): 52.01% (theoretical value for TBPD: 52.23%); hydrogen (H): 7.64%(theoretical value for TBPD: 7.70%); oxygen (O): 40.35% (theoreticalvalue for TBPD: 40.07%). The found values of elementary analysis werevery close to the theoretical values respectively. Based on theseresults, the product obtained was identified to be TBPD.

T10 of the TBPD thus obtained measured in benzene at a concentration of0.01 mol/liter was 103° C.

Example 5

Synthesis of THPD

A reaction was carried out in the same manner as in Example 4 exceptthat 152.6 g of the 70% aqueous t-butyl hydroperoxide solution wasreplaced with 144.4 g of a 97% 1,1-dimethylbutyl hydroperoxide to give353 g of a liquid. The concentration of THPD in the solution was foundto be 43.8% by measuring the amount of active oxygen, and the yield ofsynthesis based on the starting material carbonate was 75%.

The solution was treated to give a product having a purity of 93%, andthen the product was subjected to nuclear magnetic resonancespectrometry (H-NMR) to detect peaks: 0.94 ppm (6H), 1.53 ppm (4H), 4.22ppm (8H), 4.20 ppm (4H), 1.26 ppm (24H), 1.59 ppm (8H), 1,55 ppm (8H)and 0.91 ppm (12H). Further, absorption bands corresponding to C═O wereobserved at 1794 cm⁻¹ and 1763 cm⁻¹ by means of infrared (IR) absorptionspectrometry.

Elementary analysis of the product gave the following results: carbon(C): 57.01% (theoretical value for THPD: 56.53%); hydrogen (H): 8.44%(theoretical value for THPD: 8.56%); oxygen (O): 34.55% (theoreticalvalue for THPD: 34.91%). The found values of elementary analysis werevery close to the theoretical values respectively. Based on theseresults, the product obtained was identified to be THPD.

T10 of the THPD thus obtained measured in benzene at a concentration of0.01 mol/liter was 98° C.

Example 6

Bulk Polymerization of Styrene

To a glass ampoule having an inside diameter of 4 mm and a length of 300mm was introduced 2 ml of styrene containing 322 ppm (0.002 mol/kg interms of --OO-- bonds) of TBPP in terms of purity (the same shall applyhereinafter) dissolved therein. After the gas in the ampoule wasreplaced with nitrogen, the ampoule was sealed and immersed in athermostatic bath at 120° C. to effect bulk polymerization for 10 hours.After completion of polymerization, polymer conversion rate was found bydetermining the amount of residual styrene by means of gaschromatography. Further, number average molecular weight (Mn) and weightaverage molecular weight (Mw) of the resulting polymer were determinedby means of gel permeation chromatography (GPC). Results are as shown inTable 1.

Examples 7 to 9

Tests were carried out in the same manner as in Example 6, except thatTBPP employed in Example 6 was replaced with polyfunctional peroxides(0.002 mol/kg in terms of --OO-- bonds) as listed in Table 1respectively. Results are as shown in Table 1.

Example 10

A test was carried out in the same manner as in Example 6, except thathalf of TBPP (0.001 mol/kg in terms of --OO-- bonds) employed in Example6 was replaced with TBPD. Results are as shown in Table 1.

Comparative Examples 1 to 4

Tests were carried out in the same manner as in Example 6, except thatTBPP employed in Example 6 was replaced with conventional polyfunctionalperoxides (0.002 mol/kg in terms of --OO-- bonds) as listed in Table 1respectively. Results are as shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________                                     Polymer                                      Example/                                                                              Polymerization                                                                       Loading                                                                           Polymerization                                                                       Polymerization                                                                       conversion                                   Comp. Example                                                                         initiator                                                                            (ppm)                                                                             temp. (° C.)                                                                  time (h)                                                                             rate (%)                                                                           Mn  Mw                                  __________________________________________________________________________    Example 6                                                                             TBPP   322 120    10     99.5 253000                                                                            559000                              Example 7                                                                             THPP   378 120    10     98.5 256000                                                                            553000                              Example 8                                                                             TOPP   434 120    10     98.7 254000                                                                            532000                              Example 9                                                                             TBPD   379 120    10     99.4 253000                                                                            629000                              Example 10                                                                            TBPP   161 120    10     99.5 254000                                                                            601000                                      TBPD   190                                                            Comp. Ex. 1                                                                           TBCH   218 120    10     85.1 182000                                                                            380000                              Comp. Ex. 2                                                                           BBCP   280 120    10     86.9 237000                                                                            490000                              Comp. Ex. 3                                                                           TBTA   230 120    10     87.5 209000                                                                            416000                              Comp. Ex. 4                                                                           TBTM   236 120    10     88.8 224000                                                                            428000                              __________________________________________________________________________

As can be understood from Examples 6 to 10 and Comparative Examples 1 to4 shown in Table 1, in the cases where the polyfunctional peroxides ofExamples 6 to 10 were employed as polymerization initiators, the polymerconversion rates are high compared with the cases where the conventionalpolyfunctional peroxides were employed in equimolar amounts in terms ofperoxy bonds (--OO-- bonds), and high molecular weight compounds wereobtained. Such results are surmised to be brought about by the pluralityof peroxy bonds contained in the polyfunctional peroxide in each Examplewhich acted with high polymerization initiation efficiency as thepolymerization initiator.

Example 11

Copolymerization of Styrene and N-phenylmaleimide

A reaction was carried out in the same manner as in Example 6, exceptthat styrene employed in Example 6 was replaced withstyrene/N-phenylmaleimide=85:15 in terms of weight ratio. As a result,polymer conversion rate, Mn and Mw were 68.6%, 310000 and 601000respectively. The polymer thus formed was colorless.

Comparative Example 5

A reaction was carried out in the same manner as in Example 11, exceptthat TBPP employed in Example 11 was replaced with 280 ppm of BBCP as aconventional polyfunctional peroxide. As a result, polymer conversionrate, Mn and Mw were 66.0%, 282000 and 559000 respectively. The resultsof Example 11 and Comparative Example 5 demonstrated that the use ofstyrene and N-phenylmaleimide also exhibits an effect of achieving ahigh polymer conversion rate and giving a high molecular weight polymer.

Example 12

Copolymerization of α-methylstyrene and Acrylonitrile

A reaction was carried out in the same manner as in Example 6, exceptthat styrene employed in Example 6 was replaced withα-methylstyrene/acrylonitrile=85:15 in terms of weight ratio and that1608 ppm of TBPP was employed. As a result, polymer conversion rate, Mnand Mw were 68.6%, 310000 and 601000 respectively. The polymer thusformed was colorless.

Comparative Example 6

A reaction was carried out in the same manner as in Example 12, exceptthat TBPP employed in Example 12 was replaced with 1402 ppm of BBCP as aconventional polyfunctional peroxide. As a result, polymer conversionrate, Mn and Mw were 66.0%, 282000 and 559000 respectively.

The results of Example 12 and Comparative Example 6 demonstrated thatthe use of α-methylstyrene and acrylonitrile has the same effect asdescribed above.

Example 13

Copolymerization of Styrene and Butyl Acrylate

A reaction was carried out in the same manner as in Example 6, exceptthat styrene employed in Example 6 was replaced with styrene/butylacrylate=80:20 in terms of weight ratio and that 1608 ppm of TBPP wasemployed. As a result, polymer conversion rate, Mn and Mw were 99.1%,236000 and 515000 respectively.

Comparative Example 7

A reaction was carried out in the same manner as in Example 13, exceptthat TBPP employed in Example 13 was replaced with 1402 ppm of BBCP. Asa result, polymer conversion rate, Mn and Mw were 98.8%, 211000 and448000 respectively.

The results of Example 13 and Comparative Example 7 demonstrated thatthe use of styrene and butyl acrylate has the same effect as describedabove.

Example 14

Suspension Polymerization of Styrene

To a 1000 ml-capacity stainless steel autoclave were introduced 400 mlof a deionized water, 8 g of tricalcium phosphate and 0.1 g of sodiumdodecylbenzenesulfonate, followed by addition of 200 g of styrene and0.0642 g of TBPP (in terms of purity) thereto.

The gas present in the vacant space of the autoclave was replaced fullywith a nitrogen gas, and then the autoclave was hermetically sealed. Theresulting mixture was heated to 100° C. with stirring to effectpolymerization for 3 hours. The mixture was further heated to 130° C.over 5 hours and then polymerized at the same temperature for 2 hours.After completion of polymerization, the resulting mixture was cooled,filtered, washed with hydrochloric acid, rinsed with water and thendried to give 197 g of a polymer. The residual vinyl monomer wasanalyzed by means of gas chromatography (GLC) to be 0.1%. The polymerthus obtained had Mn of 186000 and Mw of 359000. Melt flow index (IM)(expressing flowability of a melt) of the polymer was measured inaccordance with JIS K-6870. The polymer was found to have an MI of 6.4(g/10 min).

Comparative Example 8

The same autoclave as employed in Example 14 was used, and the samecompounds as employed in Example 14 were introduced thereto, except that0.0642 g of TBPP was replaced with 0.0566 g of TBTM (in terms ofpurity). The resulting mixture was heated to 110° C. with stirring toeffect polymerization for 3 hours. The mixture was further heated to140° C. over 5 hours and then polymerized at the same temperature for 2hours. After completion of polymerization, the resulting mixture wascooled, filtered, washed with hydrochloric acid, rinsed with water andthen dried to give 198 g of a polymer. The polymer thus obtained had Mnof 177000 and Mw of 354000. Melt flow index (IM) of the polymer was 4.3(g/10 min).

In Example 14 and Comparative Example 8, polymers having substantiallythe same molecular weights were prepared by adjusting the amount ofpolymerization initiator employed and the polymerization temperature,and melt flow indices of the polymers were measured. The result ofExample 14 demonstrated that the polymer has a melt flow index value ofgreater than that in Comparative Example 8 and has excellent flowabilityin molding. This shows that the polymer obtained has a branchedstructure.

Example 15

Preparation of HIPS

To a 2000 ml-capacity four-necked flask equipped with a stirrer, acondenser and a nitrogen introducing pipe were introduced 1500 g of asolution of styrene containing 105 g of polybutadiene dissolved thereinand 1.5 g of TBPP. The gas present in the vacant space of the flask wasreplaced with a nitrogen gas. Subsequently, the resulting mixture waspolymerized at 100° C. with stirring at 500 rpm for 4 hours (first-steppolymerization). The amount of unreacted styrene was determined by meansof gas chromatography (GLC), and the polymer conversion rate was foundto be 40%.

Subsequently, the polymer thus obtained was transferred to a 5000ml-capacity stainless steel autoclave, to which was added 3000 ml of anaqueous solution containing 0.2% of a mixture of partly saponifiedpolyvinyl alcohol (saponification degree: 88%; polymerization degree:2400)/hydroxypropyl methyl cellulose (viscosity as a 2% aqueous solutionat 20° C.: 100 cp)=1:1 dissolved therein. After the gas present in thevacant space of the autoclave was replaced with a nitrogen gas, theautoclave was hermetically sealed. Subsequently, the resulting mixturewas heated continuously from 100 to 120° C. with stirring at 300 rpmover 4 hours to effect polymerization (second-step polymerization).After completion of polymerization, the resulting mixture was cooled,filtered and then dried to give a polymer as beads. Polymer conversionrate of styrene was 99%.

Graft efficiency of the bead-like polymer obtained was determined in thefollowing manner:

From the polymer was collected 1 g of a sample, and the sample wassubjected to extraction with methyl ethyl ketone employing a Soxhletextractor for 24 hours so as to remove homopolystyrene. The residue wasdried, and the weight of the dried residue was measured (A).

Graft efficiency was calculated employing the following expression:

    Graft efficiency (%)=(A-amount of polybutadiene used)×100/amount of polybutadiene used

Thus, the graft efficiency was calculated to be 59%. The number averagemolecular weight and weight average molecular weight of polystyreneextracted with methyl ethyl ketone was found to be 182000 and 466000respectively.

Comparative Example 9

The second-step polymerization was carried out in the same manner as inExample 15, except that 1.5 g of TBPP employed in Example 15 wasreplaced with 1.5 g of BBCP. The polymer conversion rate of styrene wasfound to be 99%, and the graft efficiency was 43%. The number averagemolecular weight and weight average molecular weight of polystyreneextracted with methyl ethyl ketone were found to be 155000 and 361000respectively.

Therefore, the present examples and embodiments are to be considered asillustrative and not restrictive, and the invention is not to be limitedto the details given herein, but may be modified within the scope of theappended claims.

What is claimed is:
 1. A polyfunctional peroxide represented by thefollowing general formula (2): ##STR8## wherein R³ represents a linearalkyl group having 1 to 3 carbon atoms; and X represents a group:##STR9## (wherein R⁴ represents a linear or branched alkyl group having1 to 5 carbon atoms).
 2. The polyfunctional peroxide represented by thegeneral formula (2) according to claim 1, wherein R³ represents an ethylgroup and R⁴ contained in X represents a methyl group.
 3. Thepolyfunctional peroxide represented by the general formula (2) accordingto claim 2, which is selected from the group consisting ofdi(2,2-bis(t-butylperoxycarbonyloxymethyl)butyl) carbonate anddi(2,2-bis(1,1-dimethylbutylperoxycarbonyloxymethyl) butyl) carbonate.